Absolute rate constants for the reactions ofOHradicals withCH3CH2OH, CF2HCH2OHandCF3CH2OH

Summary Pulsed laser photolysis with resonance fluorescence monitoring of OH radicals was applied at T = 300±2 K to obtain the rate constants of k₁= (3.38±0.60)x10^-12, k₂= (2.52±0.44)x10^-13and k₃ = (1.06±0.30)x10^-13cm³molecule^-1s^-1with 2σprecision given for the overall reactions OH + CH₃CH₂OH (1), OH + CF₂HCH₂OH (2) and OH + CF₃CH₂OH (3), respectively. k₂is the first direct kinetic data for the reaction of OH radicals with CF₂HCH₂OH reported in the literature.</o:p>     

Colloidal structures in natural oils

Natural oils are in general mixtures of triglycerides of various fatty acids containing also small quantities of a multitude of other molecules, the minor components. Their composition depends on the type of their sources, either vegetable or animal, and on agronomic and climatic conditions. Extraction process highly influences the final composition of the natural oils. The bulk triglyceride phase presents some structural order due to the internal polarity of these molecules. The presence of the minor components, which are either amphiphilic or even hydrophilic together with some remaining moisture, induces colloidal association within the lipophilic triglyceride phase. These local organizates host proteins and antioxidants that preserve their activity influencing the quality and stability of the edible oils. Of specific interest is the case of the veiled virgin olive oil, the untreated juice of the olives. Veiled virgin olive oil is unique among vegetable oils that is consumed without any refining process and consequently possesses colloidal structure. It is remarkable that this unfiltered oil presents higher resistance to oxidation than the filtered ones, indicating the significance of internal structure to the final quality of the product.     

Crystallization and enzymatic degradation of novel poly(ε-caprolactone-co-propylene succinate) copolymers

A series of novel poly(ε-caprolactone-co-propylene succinate) P(CL-co-PSu) copolymers having low propylene succinate content and high molecular weight were synthesized following a combinatory scheme of ring opening and polycondensation reactions, in an attempt to obtain copolymers of sufficient performance and increased biodegradation rates. Enzymatic hydrolysis of the copolymers was studied in the presence of mixture of Rhizopus delemar and Pseudomonas cepacia lipases. Much higher hydrolysis rates, comparing to neat PCL, were proved by both mass loss measurements and scanning electron microscopy (SEM) observations of the degraded film surfaces. Thermodynamics of cocrystallization and wide-angle X-ray diffraction (WAXD) patterns were investigated to estimate the extent of comonomer cocrystallization. Results of the study showed that comonomer inclusion may hold, though the molar fraction of the comonomer in the PCL crystals is lower than in the bulk. This means that not only the observed decrease of the degree of crystallinity from about 48% for PCL to about 29% for the P(CL-co-PSu) 75/25 favours enzymatic hydrolysis, but also the enrichment of the amorphous phase in the fast degrading propylene succinate units plays its role. The non-isothermal crystallization rates of the copolymers, like the melting points, decreased substantially when the propylene succinate content exceeded 8 mol%. The activation energy of crystallization was calculated using the isoconversional method of Friedman, over the whole range of crystallization temperatures. An increase was found in the activation energy with increasing the comonomer content in the copolymers also proving the reduced symmetry along the copolymer chains due to the presence of comonomer units.     

Berth allocation at indented berths for mega-containerships

This paper addresses the berth allocation problem at a multi-user container terminal with indented berths for fast handling of mega-containerships. In a previous research conducted by the authors, the berth allocation problem at a conventional form of the multi-user terminal was formulated as a nonlinear mathematical programming, where more than one ship are allowed to be moored at a specific berth if the berth and ship lengths restriction is satisfied. In this paper, we first construct a new integer linear programming formulation for easier calculation and then the formulation is extended to model the berth allocation problem at a terminal with indented berths, where both mega-containerships and feeder ships are to be served for higher berth productivity. The berth allocation problem at the indented berths is solved by genetic algorithms. A wide variety of numerical experiments were conducted and interesting findings were explored.     

Using clathrate hydrates for gas storage and gas-mixture separations: experimental and computational studies at multiple length scales

ABSTRACT

Clathrate hydrates have characteristic properties that render them attractive for a number of industrial applications. Of particular interest are the following two cases: (i) the incorporation of large amounts of gas molecules into the solid structure has resulted in considering hydrates as possible material for the storage/transportation of energy or environmental gases, and (ii) the selective incorporation of guest molecules into the solid structure has resulted in considering hydrates for gas-mixture separations. For the proper design of such industrial applications, it is essential to know accurately a number of thermodynamic, structural and transport properties. Such properties can either be measured experimentally or calculated at different scales that span the molecular scale-up to the continuum scale. By using clathrate hydrates as a particular case study, we demonstrate that performing studies at multiple length scales can be utilised in order to obtain properties that are essential to process design.